1,9-diazaphenalene derivative and process for manufacturing the same

ABSTRACT

A 1,9-diazaphenalene derivative is represented by 
     
       
         
         
             
             
         
       
     
     where R, R 1 , R 2 , R 3 , Y 1 , and Y 2  are as defined in the specification and claims. The 1,9-diazaphenalene derivative may emit fluorescence after being excited, and is thus suitable for use as a fluorescent material for an organic light emitting diode. A method for preparing the 1,9-diazaphenalene derivative is also disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority of Taiwanese Application No. 103145258, filed on Dec. 24, 2014.

FIELD

The disclosure relates to a 1,9-diazaphenalene derivative, and more particularly to a 1,9-diazaphenalene derivative which is highly substituted. The disclosure also relates to a process for manufacturing the 1,9-diazaphenalene derivative.

BACKGROUND

Taiwanese Patent Publication No. 263510 discloses 1,8-benzo[b]naphthyridine derivative in which three aromatic rings are fused in a linear manner. The derivative is useful as an antimicrobial agent.

It is disclosed in J. Org. Chem., 1990, 55, 6140-6147 a 1H-2,3-dihydro-1,9-diazaphenalene derivative of the following formula:

where Ar represents phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-fluorophenyl, and R represents hydrogen or benzyl. As shown in the above formula, not all of three fused cyclic moieties are aryl rings.

There is a need in the art for a 1,9-diazaphenalene derivative which contains a plurality of fused aryl rings and which is highly substituted.

SUMMARY

Therefore, an object of the disclosure is to provide a 1,9-diazaphenalene derivative which contains a plurality of fused aryl rings, which is highly substituted, and which may emit fluorescence after being excited.

Another object of the disclosure is to provide a process for manufacturing the 1,9-diazaphenalene derivative.

A 1,9-diazaphenalene derivative according to a first aspect of the disclosure is represented by formula (III)

where

each R independently represents a C₁-C₁₀ linear or branched alkyl group, or a 5-6 membered aryl or heteroaryl group which is unsubstituted or substituted with a C₁-C₁₀ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ haloalkyl group or a halo group;

each of R¹, R², and R³ independently represents hydrogen, a C₁-C₁₀ linear or branched alkyl group, a C₁-C₁₀ alkoxy group, a C₁-C₆ haloalkyl group, an unsubstituted or C₁-C₁₀ alkyl group-substituted amino group, a halo group, a C₆-C₁₈ aryl group,

in which R⁴ represents a C₁-C₁₀ alkyl group, or

in which R⁵ represents hydrogen or a C₁-C₁₀ alkyl group;

Y¹ represents hydrogen, or a C₁-C₁₀ linear or branched alkyl group;

Y² represents R; or

Y¹ and Y² are combined to forma 6-membered ring moiety represented by

where

each of R⁶ and R⁷ independently represents a thio group, a heteroalkyl group, or a C₁-C₁₀ linear or branched alkyl group, or R⁶ and R⁷ are combined to form a 5-6 membered aryl or heteroaryl group represented by

which is unsubstituted or substituted with a C₁-C₁₀ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ haloalkyl group or a halo group.

A process for manufacturing the 1,9-diazaphenalene derivative of the aforesaid formula (III) according to a second aspect of the disclosure includes the step of subjecting a benzamidine derivative of formula (I)

where

X represents hydrogen, hydroxyl, or a C₁-C₁₀ linear or branched alkyl group; and

R¹, R², and R³ are defined as above,

and an alkyne compound of formula (II)

where R is defined as above,

to a catalystic reaction in the presence of an oxidant and a catalyst selected from the group consisting of a rhodium-containing complex and a ruthenium-containing complex.

A process for manufacturing the 1,9-diazaphenalene derivative of the aforesaid formula (III) according to a third aspect of the disclosure includes the step of subjecting a benzonitrile compound of formula (IV)

where R¹, R², and R³ are defined as above,

an amine compound of formula X—NH₂ (V), where X is defined as above, and an alkyne compound of formula (II)

where R is defined as above,

to a catalystic reaction in the presence of an oxidant and a catalyst selected from the group consisting of a rhodium salt and a ruthenium salt.

A 1,9-diazaphenalene derivative which contains a plurality of fused aryl rings, which is highly substituted, and which may emit fluorescence after being excited may be manufactured in a high yield by the disclosure via a simple one-pot reaction.

BRIEF DESCRIPTION OF THE DRAWINGS

Other features and advantages of the disclosure will become apparent in the following detailed description of the embodiments with reference to the accompanying drawing, of which:

FIG. 1 is an ultraviolet-visible spectrum illustrating absorption and fluorescence spectra of 1,9-diazaphenalene derivatives obtained in Examples 9, 10, 12 and 18.

DETAILED DESCRIPTION

A 1,9-diazaphenalene derivative according to the disclosure is represented by

where

each R independently represents a C₁-C₁₀ linear or branched alkyl group, or a 5-6 membered aryl or heteroaryl group which is unsubstituted or substituted with a C₁-C₁₀ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ haloalkyl group or a halo group;

each of R¹, R², and R³ independently represents hydrogen, a C₁-C₁₀ linear or branched alkyl group, a C₁-C₁₀ alkoxy group, a C₁-C₆ haloalkyl group, an unsubstituted or C₁-C₁₀ alkyl group-substituted amino group, a halo group, a C₆-C₁₈ aryl group,

in which R⁴ represents a C₁-C₁₀ alkyl group, or

in which R⁵ represents hydrogen or a C₁-C₁₀ alkyl group;

Y¹ represents hydrogen, or a C₁-C₁₀ linear or branched alkyl group;

Y² represents R; or

Y¹ and Y² are combined to forma 6-membered ring moiety represented by R

where

each of R⁶ and R⁷ independently represents a thio group, a heteroalkyl group, or a C₁-C₁₀ linear or branched alkyl group, or R⁶ and R⁷ are combined to form a 5-6 membered aryl or heteroaryl group represented by

which is unsubstituted or substituted with a C₁-C₁₀ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ haloalkyl group or a halo group.

A process for manufacturing the 1,9-diazaphenalene derivative of the aforesaid formula (III) according to the disclosure includes the step of subjecting a benzamidine derivative of formula (I)

where

X represents hydrogen, hydroxyl, or a C₁-C₁₀ linear or branched alkyl group; and

R¹, R², and R³ are defined as above,

and an alkyne compound of formula (II)

where R is defined as above to a catalystic reaction in the presence of an oxidant and a catalyst selected from the group consisting of a rhodium-containing complex and a ruthenium-containing complex.

Alternatively, a process for manufacturing the 1,9-diazaphenalene derivative of the aforesaid formula (III) according to the disclosure includes the step of subjecting a benzonitrile compound of formula (IV)

where R¹, R², and R³ are defined as above,

an amine compound of formula X—NH₂ (V), where X is defined as above, and an alkyne compound of formula (II),

where R is defined as above, to a catalystic reaction in the presence of an oxidant and a catalyst selected from the group consisting of a rhodium salt and a ruthenium salt.

Preferably, each R independently represents a 5-6 membered aryl or heteroaryl group which is unsubstituted or substituted with a C₁-C₁₀ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ haloalkyl group or a halo group.

More preferably, each R is independently selected from the group consisting of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-bromophenyl, 4-trifluoromethylphenyl and 2-thienyl.

In the process for manufacturing the 1,9-diazaphenalene derivative of formula (III), a molar ratio of the benzamidine derivative of formula (I) to the alkyne compound of formula (II) ranges preferably from 1:2 to 1:3.5 and more preferably from 1:3 to 1:3.5.

Preferably, the oxidant suitable for the disclosure is copper (II) compounds, such as copper (II) acetate, copper (II) acetate monohydrate and copper trifluoromethanesulfonate.

Preferably, the rhodium-containing complex suitable for the disclosure is a rhodium (III)-containing complex selected from the group consisting of [Cp*Rh(CH₃CN)₃](SbF₆)₂ and [RhCp*Cl₂]₂, wherein Cp* represents pentamethylcyclopentadienyl.

Preferably, the ruthenium-containing complex is a ruthenium (II)-containing complex of [RuCl₂(p-cymene)]₂, wherein Cp* represents pentamethylcyclopentadienyl.

Preferably, the catalystic reaction is conducted in the presence of an organic solvent. The organic solvent suitable for the disclosure is selected from the group consisting of 2-methyl-2-butanol, dimethylformamide, o-xylene, dichloroethane, acetonitrile and acetic acid.

Preferably, X in formula (I) or formula (V) represents hydroxyl.

Preferably, the catalystic reaction is conducted at a temperature ranging from 120° C. to 130° C.

Preferably, the catalystic reaction is conducted for a period ranging from 18 hours to 42 hours.

A reaction scheme of the process for manufacturing the 1,9-diazaphenalene derivative of formula (III) is illustrated below, in which a rhodium (III)-containing complex is used as the catalyst, Cp* represents pentamethylcyclopentadienyl, X in formula (I) represents hydroxyl, and R in formula (II) represents phenyl,

The following examples are provided to illustrate the embodiments of the disclosure, and should not be construed as limiting the scope of the disclosure.

Synthesis (I) of 1,9-Diazaphenalene Derivative Examples 1-23

0.25 mmol of a benzamidine derivative of formula (I), 0.80 mmol of an alkyne compound of formula (II), 6.0 mol % of [Cp*Rh(CH₃CN)₃](SbF₆)₂ (Cp* represents pentamethylcyclopentadienyl), and 1.12 mmol (4.5 equivalents) of copper (II) acetate were added into a sealed tube. The sealed tube was then evacuated and purged with nitrogen gas three times. 3.5 ml of 2-methyl-2-butanol was subsequently added into the sealed tube via a syringe under a nitrogen atmosphere to obtain a reaction mixture, which was stirred at 130° C. for 18 hours. The mixture was then cooled and diluted with CH₂Cl₂ (10 ml), followed by filtration through a Celite pad. The Celite pad was washed with CH₂Cl₂ (50 ml) to obtain a filtrate. The filtrate was concentrated in vacuo and the residue was purified by a silica gel column using hexane-EtOAc (5-15%) as eluent to give a product of formula (III).

The definitions of R¹, R², R³, X, R, Y¹, and Y² in formulae (I), (II), and (III) in Examples 1-23 are listed in Table 1.

TABLE 1 Formulae Formula (I) (II) and (III) Formula (III) Ex. R¹ R² R³ X R R¹ R² R³ Y¹ and Y²  1  2  3  4  5  6  7  8  9 10 H H H H H H H H H H H Me tBu OMe F Cl Br I CF₃ N(Me)₂ H H H H H H H H H H OH OH OH OH OH OH OH OH OH OH Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph H H H H H H H H H H H Me tBu OMe F Cl Br I CF₃ N(Me)₂ H H H H H H H H H H

11 H Ph H OH Ph H Ph H 12 OMe OMe OMe OH Ph OMe OMe OMe 13 OMe H H OH Ph OMe H H H H OMe 14 15 16 17 H H H H H H H H H H H H OH OH OH OH 4-MeC₆H₄ 4-MeOC₆H₄ 4-BrC₆H₄ 4-CF₃C₆H₄ H H H H H H H H H H H H

Z = Me Z = OMe Z = Br Z = CF₃ 18 H H H OH 2-thienyl H H H

19 H Me H OH Et H Me H Y¹ = H Y² = Et 20 H Me H OH Pr H Me H Y² = Pr 21 H Me H OH Bu H Me H Y² = Bu 22 H H H H Ph H H H

23 H H H Me Ph H H H Y¹ = Me; Y² = Ph

The products obtained in Examples 1-23 were identified and the results are shown below.

Example 1

Yield: 83%; scarlet red solid; m.p. 265-268° C.; ¹H NMR (500 MHz, CDCl₃): δ 7.52-7.50 (m, 5H), 7.47-7.38 (m, 2H), 7.28-7.19 (m, 10H), 7.12-7.06 (m, 5H), 7.05-6.96 (m, 5H), 6.92-6.88 (m, 2H), 6.80 (td, J=8.0, 2.0 Hz, 1H), 6.50-6.49 (m, 2H); ¹³C NMR (125 MHz, CDCl₃): δ 150.0, 149.3, 140.5, 138.6, 137.8, 137.6, 136.9, 136.8, 135.6, 135.2, 134.6, 131.8, 131.7, 131.2, 130.9, 130.2, 130.0, 129.7, 128.5, 128.2, 127.9, 126.9, 126.7, 126.6, 126.5, 125.9, 125.5, 124.9, 123.2, 121.8, 118.9, 117.5; HRMS (FAB⁺) m/z: MH⁺ calculated for C₄₉H₃₂N₂: 648.2565. found: 648.2563; IR (KBr): 3054, 2929, 2337, 1342 cm⁻¹.

Example 2

Yield: 78%; orange solid; m.p. 294-297° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.51-7.45 (m, 5H), 7.26-7.17 (m, 8H), 7.07-6.95 (m, 11H) 6.93-6.86 (m, 3H), 6.77 (td, J=7.2, 1.2 Hz, 1H), 6.71 (s, 1H), 6.45 (d, J=7.2 Hz, 2H), 2.27 (s, 3H); ¹³C NMR (125 MHz, CDCl₃): δ 150.2, 149.3, 141.4, 140.7, 138.8, 138.0, 137.9, 137.4, 137.1, 136.9, 135.8, 135.2, 134.6, 131.9, 131.8, 131.3, 130.2, 130.1, 129.8, 128.5, 128.3, 128.2, 127.9, 127.8, 127.5, 127.0, 126.7, 126.6, 126.5, 125.8, 125.4, 124.9, 122.8, 120.4, 119.0, 118.8, 22.6; HRMS (EI⁺) calculated for C₅₀H₃₄N₂: 662.2722. found: 662.2724; IR (KBr): 3054, 2931, 2337, 1342 cm⁻¹.

Example 3

Yield: 70%; orange solid; m.p. 325-328° C.; ¹H NMR (500 MHz, CDCl₃): δ 7.53-7.42 (m, 5H), 7.26-7.18 (m, 8H), 7.13-7.02 (m, 10H), 6.99-6.98 (m, 3H), 6.97-6.86 (m, 2H), 6.78 (tt, J=8.5, 1.5 Hz, 1H), 6.47-6.44 (m, 2H), 1.16 (s, 9H); ¹³C NMR (125 MHz, CDCl₃): δ 154.1, 150.1, 149.1, 140.7, 138.7, 137.9, 137.5, 137.4, 137.1, 137.0, 135.5, 134.8, 134.6, 131.9, 131.7, 131.2, 130.3, 129.6, 128.6, 128.2, 128.1, 127.9, 127.8, 127.5, 127.0, 126.7, 126.6, 126.5, 126.4, 125.8, 125.3, 124.8, 123.3, 120.3, 119.2, 116.1, 115.0, 35.4, 31.0; HRMS (EI⁺) calculated for C₅₃H₄₀N₂: 704.3191. found: 704.3188; IR (KBr): 3054, 2931, 2337 1319 cm⁻¹.

Example 4

Yield: 66%, orange solid; m.p. 289-293° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.50-7.42 (m, 5H), 7.27-7.16 (m, 8H), 7.10-7.00 (m, 9H), 6.98-6.86 (m, 4H), 6.79 (td, J=8.4, 2.0 Hz, 1H), 6.60 (d, J=2.4 Hz, 1H), 6.46 (d, J=2.4 Hz, 1H), 6.45 (d, J=7.2 Hz, 2H), 3.64 (s, 3H); ¹³C NMR (125 MHz, CDCl₃): δ 161.9, 150.6, 148.9, 140.7, 139.8, 138.6, 138.0, 137.4, 137.3, 136.9, 136.4, 134.6, 131.8, 131.7, 131.1, 130.2, 130.0, 129.8, 128.6, 128.3, 128.0, 127.8, 127.3, 127.0, 126.7, 126.5, 125.8, 125.3, 124.9, 122.8, 118.4, 117.7, 107.1, 100.1, 55.1; HRMS (EI⁺) calculated for C₅₀H₃₄N₂O: 678.2671. found: 678.2671; IR (KBr): 3054, 2923, 2337, 1350, 1123 cm⁻¹.

Example 5

Yield: 86%; scarlet red solid; m.p. 196-200° C.; ¹H NMR (500 MHz, CDCl₃): δ 7.55-7.46 (m, 5H), 7.28-7.19 (m, 9H), 7.14-6.98 (m, 11H), 6.93-6.90 (m, 2H), 6.84-6.80 (m, 1H), 6.59 (d, J=10.0, 2.5 Hz, 1H), 6.48-6.46 (m, 2H); ¹³C NMR (125 MHz, CDCl₃): δ 164.9 (d_(C-F), J=246.1 Hz), 151.0, 148.9, 140.1 (d_(C-F), J=11.0 Hz), 138.5 (d_(C-F), J=11.0 Hz), 138.2, 137.4, 137.2, 136.9, 136.7, 134.5, 131.7, 131.6, 131.0, 130.1, 130.0, 128.6, 128.4, 128.2, 127.8, 127.0, 126.9, 126.8, 126.6, 126.0, 125.9, 125.0, 123.1 (d, J=4.5 Hz), 119.0, 118.3, 105.7 (d_(C-F), J=27.6 Hz), 103.5 (d_(C-F), J=24.2 Hz); HRMS (EI⁺) calculated for C₄₉H₃₁FN₂: 666.2471. found: 666.2460; IR (KBr): 3054, 2932, 1350, 1126 cm⁻¹.

Example 6

Yield: 75%; orange solid; m.p. 284-287° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.55-7.47 (m, 5H), 7.27-7.19 (m, 9H), 7.15-6.90 (m, 11H), 6.89 (t, J=7.6 Hz, 2H), 6.86-6.82 (m, 2H), 6.46 (d, J=8.4 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ 151.2, 149.1, 140.2, 139.0, 138.1, 138.0, 137.3, 137.2, 137.0, 136.8 136.7, 134.5, 131.8, 131.8, 131.6, 131.1, 130.2, 130.1, 128.7, 128.6, 128.5, 128.3, 127.9, 127.1, 126.8, 126.7, 126.1, 126.0, 125.1, 122.6, 120.1, 118.0, 117.7, 117.3; HRMS (EI⁺) calculated for C₄₉H₃₁ClN₂: 682.2176. found: 682.2174; IR (KBr): 3054, 2923, 1342, 1126, 995 cm⁻¹.

Example 7

Yield: 72%; scarlet red solid; m.p. 310-312° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.55-7.47 (m, 5H), 7.29-7.17 (m, 9H), 7.12-6.94 (m, 12H), 6.89 (t, J=7.2 Hz, 2H), 6.81 (td, J=6.4, 2.0 Hz, 1H), 6.45 (d, J=8.4 Hz, 2H); ¹³C NMR (125 MHz, CDCl₃): δ 165.9, 163.9, 151.0, 149.0, 140.2, 140.1, 138.5, 138.4, 138.2, 137.4, 137.2, 137.0, 136.7, 134.5, 131.7, 131.6, 131.0, 130.2, 130.0, 128.6, 128.4, 128.2, 127.8, 127.0, 126.9, 126.8, 126.6, 126.0, 125.9, 125.0, 123.1, 119.0, 118.3, 105.6, 103.6, 103.4; HRMS (EI⁺) calculated for C₄₉H₃₁BrN₂: 726.1671. found: 726.1640; IR (KBr): 3054, 2931, 1565, 1334, 956 cm⁻¹.

Example 8

Yield: 78%; orange solid; m.p. 236-240° C.; ¹H NMR (500 MHz, CDCl₃): δ 7.55-7.46 (m, 5H), 7.28-7.16 (m, 9H), 7.14-6.98 (m, 12H), 6.92-6.89 (m, 2H), 6.81 (td, J=6.4, 2.0 Hz, 1H), 6.47-6.46 (m, 2H); ¹³C NMR (125 MHz, CDCl₃): δ 151.0, 149.2, 140.2, 139.1, 138.0, 137.1, 136.8, 136.6, 134.4, 131.7, 131.6, 131.1, 130.1, 130.0, 128.6, 128.5, 128.3, 127.8, 127.2, 127.1, 127.0, 126.8, 126.7, 126.0, 125.7, 125.0, 121.9, 120.5, 117.6, 99.8; HRMS (EI⁺) calculated for C₄₉H₃₁IN₂: 774.1532. found: 774.1526; IR (KBr): 3054, 2923, 1560, 1342, 950 cm⁻¹.

Example 9

Yield: 63%; orange solid; m.p. 277-279° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.55-7.48 (m, 5H), 7.41 (s, 1H), 7.29-7.20 (m, 8H), 7.15-6.98 (m, 12H), 6.91 (t, J=8.0 Hz, 2H), 6.82 (td, J=8.4, 2.4 Hz, 1H), 6.47 (d, J=8.4 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ 151.3, 149.0, 140.0, 137.9, 137.6, 137.0, 136.9, 136.6, 136.5, 134.4, 132.9, 132.6, 132.2, 131.7, 131.5, 131.0, 130.8, 130.1, 129.9, 129.0, 128.7, 128.6, 128.5, 128.4, 127.9, 127.4, 127.2, 127.1, 126.8, 126.7, 126.2, 126.1, 125.1, 123.7, 122.4, 118.5, 115.5, 112.9; HRMS (EI⁺) calculated for C₅₀H₃₁F₃N₂: 716.2439. found: 716.2443; IR (KBr): 3062, 2923, 2337, 1319 cm⁻¹.

Example 10

Yield: 68%; red solid; m.p. 259-261° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.54-7.42 (m, 5H), 7.26-7.14 (m, 8H), 7.13-6.94 (m, 11H), 6.87 (d, J=7.2 Hz, 2H), 6.78 (td, J=8.4, 1.6 Hz, 1H), 6.44 (d, J=8.4 Hz, 2H), 6.38 (dm, J=2.0 Hz, 1H), 6.34 (dm, J=2.0 Hz, 1H), 2.79 (s, 6H); ¹³C NMR (125 MHz, CDCl₃): δ 152.1, 150.2, 148.9, 141.1, 149.3, 139.0, 138.6, 137.5, 137.1, 136.4, 136.0, 134.7, 131.7, 131.3, 130.2, 130.0, 129.6, 128.5, 128.2, 128.0, 127.8, 127.4, 126.9, 126.6, 126.3, 126.2, 125.6, 124.7, 121.9, 118.7, 115.4, 104.7, 99.2, 40.1; HRMS (EI⁺) calculated for C₅₁H₃₇N₃: 691.2987. found: 691.2998; IR (KBr): 3054, 2923, 2337, 1357 cm⁻¹.

Example 11

Yield: 81%; red solid; m.p. 284-288° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.58-7.40 (m, 6H), 7.37-7.21 (m, 12H), 7.15-6.97 (m, 12H), 6.91 (td, J=7.6, 2.0 Hz, 2H), 6.81 (td, J=6.8, 1.6 Hz, 2H), 6.44 (d, J=8.4 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ 150.5, 149.3, 143.8, 141.4, 140.6, 138.6, 138.0, 137.7, 137.0, 136.9, 135.8, 134.6, 132.5, 131.8, 131.7, 131.2, 130.2, 130.1, 129.9, 129.6, 129.1, 129.0, 128.7, 128.6, 128.3, 128.0, 127.8, 127.7, 127.6, 127.5, 127.4, 127.2, 127.0, 126.8, 126.7, 123.4, 121.0, 119.0, 117.4, 116.9; HRMS (EI⁺) calculated for C₅₅H₃₆N₂: 724.2878. found: 724.2879; IR (KBr): 3054, 2932, 2337, 1343 cm⁻¹.

Example 12

Yield: 81%; scarlet red solid; m.p. 300-304° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.46-7.36 (m, 5H), 7.23-7.17 (m, 6H), 7.07-6.96 (m, 11H), 6.91 (td, J=7.2, 1.6 Hz, 2H), 6.84 (t, J=7.6 Hz, 2H), 6.60 (d, J=8.0 Hz, 1H), 6.35 (d, J=8.4 Hz, 2H), 3.83 (s, 3H), 3.28 (s, 3H) 3.20 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 151.0, 150.7, 149.1, 146.3, 146.0, 140.8, 140.3, 140.2, 137.3, 136.9, 136.8, 134.9, 134.4, 131.9, 131.4, 131.1, 131.0, 130.7, 130.1, 130.0, 129.9, 129.5, 129.1, 129.0, 128.8, 128.7, 126.8, 128.4, 128.0, 127.8, 127.5, 127.3, 127.0, 126.9, 126.7, 126.6, 126.3, 125.6, 125.3, 124.9, 122.9, 121.4, 121.0, 117.3, 61.2, 60.7, 60.4; HRMS (EI⁺) calculated for C₅₂H₃₈N₂O₃: 738.2882. found: 738.2886; IR (KBr): 3054, 2932, 2337, 1343, 1203 cm⁻¹.

Example 13

Yield: 70% (a total yield of two isomers); red solid; m.p. 196-200° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.50-7.39 (m, 11H), 7.37-7.24 (m, 12H), 7.19-7.01 (m, 12H), 6.99-6.89 (m, 10H), 6.82-6.74 (m, 3H), 6.49 (d, J=8.4 Hz, 2H), 6.36 (d, J=8.8 Hz, 2H), 3.38 (s, 3H), 3.37 (s, 2H); ¹³C NMR (100 MHz, CDCl₃): δ 151.5, 150.3, 149.8, 149.3, 148.1, 140.8, 140.7, 140.5, 138.7, 137.7, 137.5, 137.3, 137.1, 137.0, 136.9, 136.6, 135.0, 134.6, 132.3, 131.9, 131.7, 131.2, 130.9, 130.3, 130.2, 129.7, 129.0, 128.8, 128.6, 128.5, 128.4, 128.2, 128.1, 127.8, 127.7, 127.6, 127.5, 127.2, 127.0, 126.9, 126.8, 126.7, 126.6, 126.5, 126.4, 126.1, 125.8, 125.6, 125.4, 125.1, 124.7, 124.5, 124.3, 123.9, 119.6, 118.6, 116.7, 112.8; HRMS (EI⁺) calculated for C₅₀H₃₄N₂O: 678.2671. found: 678.2682; IR (KBr): 3054, 2929, 2336, 1342, 1205 cm⁻¹.

Example 14

Yield: 76%; orange solid; m.p. 246-250° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.36 (t, J=7.6 Hz, 2H), 7.30 (t, J=7.6 Hz, 2H), 7.13-7.07 (m, 7H), 6.95 (d, J=8.0 Hz, 4H), 6.90-6.79 (m, 6H), 6.72 (d, J=8.0 Hz, 2H), 6.62 (d, J=8.0 Hz, 1H), 6.40 (d, J=8.0 Hz, 2H), 2.45 (s, 3H), 2.34 (s, 3H), 2.31 (s, 3H), 2.21 (s, 3H), 2.16 (s, 3H), 2.13 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 149.8, 149.4, 137.9, 137.4, 137.3, 136.0, 135.9, 135.8, 135.6, 135.1, 134.8, 134.2, 134.1, 131.7, 131.6, 131.0, 130.6, 130.4, 130.1, 129.0, 128.5, 128.4, 127.6, 127.4, 126.9, 125.1, 125.0, 122.6, 121.5, 118.5, 117.9, 116.9, 21.4, 21.3, 21.2, 21.0; HRMS (EI⁺) calculated for C₅₅H₄₄N₂: 732.3504. found: 732.3501 IR (KBr): 3054, 2923, 2337, 1342 cm⁻¹.

Example 15

Yield: 80%; orange solid; m.p. 296-299° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.39-7.34 (m, 3H), 7.15-6.98 (m, 9H), 6.94 (d, J=8.4 Hz, 1H), 6.83-6.80 (m, 5H), 6.59-6.52 (m, 5H), 6.46 (d, J=8.4 Hz, 2H), 6.40 (d, J=8.4 Hz, 1H), 3.88 (s, 3H), 3.79 (s, 3H), 3.78 (s, 3H), 3.68 (s, 3H), 3.66 (s, 3H), 3.60 (s, 3H); ¹³C NMR (125 MHz, CDCl₃): δ 159.1, 159.0, 158.2, 158.1, 157.9, 149.5, 149.3, 138.0, 137.8, 136.8, 135.7, 133.4, 132.8, 132.7, 132.2, 131.5, 130.9, 130.7, 130.4, 130.0, 129.6, 129.3, 122.0, 121.1, 120.9, 118.2, 116.7, 115.2, 113.8, 113.3, 112.4, 112.2, 109.0, 55.2, 55.1, 55.0, 54.9; HRMS (EI⁺) calculated for C₅₅H₄₄N₂O₆: 828.3199. found: 828.3204; IR (KBr): 3054, 2923, 2337, 1342 cm⁻¹.

Example 16

Yield: 73%; red solid; m.p. 254-258° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.64 (t, J=8.4 Hz, 2H), 7.45-7.40 (m, 6H), 7.33 (d, J=8.4 Hz, 2H), 7.14-7.09 (m, 6H), 6.99 (dd, J=8.8, 2.8 Hz, 4H), 6.92 (d, J=8.0 Hz, 2H), 6.88-6.79 (m, 2H), 6.33 (d, J=8.4 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ 148.8, 148.7, 138.7, 137.7, 137.3, 136.8, 135.9, 135.8, 135.3, 134.6, 134.4, 133.3, 133.2, 133.1, 132.7, 131.8, 131.7, 131.6, 131.5, 131.3, 131.0, 130.4, 130.3, 130.0, 129.6, 127.3, 125.6, 123.4, 122.8, 122.4, 121.7, 121.6, 121.4, 121.3, 120.9, 119.5, 118.4, 118.0; HRMS (EI⁺) m/z: MH⁺ calculated for C₄₉H₂₆Br₆N₂: 1115.7196. found: 1122.7220; IR (KBr): 3054, 2923, 2337, 1342 cm⁻¹.

Example 17

Yield: 68%; orange solid; m.p. 282-284° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.83 (d, J=8.4 Hz, 2H), 7.64 (d, J=8.0 Hz, 2H), 7.64 (dd, J=8.0, 2.0 Hz, 4H), 7.50 (t, J=8.0 Hz, 1H), 7.28 (d, J=8.0 Hz, 2H), 7.24-7.10 (m, 11H), 7.02 (d, J=8.4 Hz, 1H), 6.89 (d, J=7.6 Hz, 1H), 6.53 (d, J=8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃): δ 148.8, 148.6, 142.9, 141.6, 140.4, 139.9, 138.8, 138.1, 137.3, 134.3, 134.2, 132.0, 131.9, 131.4, 131.1, 130.9, 130.8, 130.3, 130.2, 129.9, 129.8, 129.6, 129.5, 129.4, 129.2, 129.1, 127.3, 127.2, 125.8, 125.7, 125.5, 125.3, 124.2, 124.1, 123.5, 123.4, 123.3, 122.6, 122.1, 121.6, 121.5, 120.2, 119.8, 118.9; HRMS (EI⁺) m/z: MH⁺ calculated for C₅₅H₂₆F₁₈N₂: 1056.1809. found: 1057.2000, IR (KBr): 3054, 2923, 2337, 1342 cm⁻¹.

Example 18

Yield: 60%; scarlet red solid; m.p. 226-230° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.66 (d, J=5.2 Hz, 1H), 7.50 (d, J=5.2 Hz, 1H), 7.42 (t, J=8.4 Hz, 1H), 7.32 (d, J=5.2 Hz, 1H), 7.28 (t, J=3.2 Hz, 1H) 7.20-7.17 (m, 3H), 7.13-7.04 (m, 4H), 7.01-6.98 (m, 2H), 6.89 (d, J=3.6 Hz, 1H), 6.78-6.76 (m, 2H), 6.73 (t, J=4.0 Hz, 1H), 6.65 (t, J=4.0 Hz, 1H), 6.56 (d, J=3.6 Hz, 1H); ¹³C NMR (125 MHz, CDCl₃): δ 150.7, 144.7, 143.8, 140.0, 139.2, 138.4, 137.6, 137.5, 137.0, 135.8, 135.5, 132.6, 131.6, 130.8, 130.2, 129.3, 129.1, 129.0, 128.9, 128.4, 127.9, 127.8, 127.3, 126.6, 126.0, 125.4, 124.1, 119.4, 118.4, 118.2, 116.7, 114.1, 105.5; HRMS (EI⁺) calculated for C₃₇H₂₀N₂S₆: 683.9951. found: 683.9952; IR (KBr): 3100, 2923, 2337, 1357 cm⁻¹.

Example 19

Yield: 72%; yellow solid; m.p. 86-90° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.18 (s, 1H), 6.77 (s, 1H), 2.83-2.75 (m, 4H), 2.55-2.45 (m, 7H), 1.29-1.24 (m, 6H), 1.98-1.12 (m, 6H); ¹³C NMR (100 MHz, CDCl₃): δ 157.2, 154.4, 152.9, 142.0, 138.5, 133.1, 122.3, 117.3, 115.0, 113.9, 112.9, 28.1, 24.0, 22.9, 20.4, 19.3, 14.6, 14.1, 13.0, 12.7; HRMS (ESI⁺) calculated for [C₂₀H₂₆N₂+H]⁺: 295.2174. found: 295.2176; IR (KBr): 2954, 2923, 1643, 1234 cm⁻¹.

Example 20

Yield: 80%; yellow solid; m.p. 126-130° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.16 (s, 1H), 6.75 (s, 1H), 2.77-2.71 (m, 4H), 2.51-2.41 (m, 7H), 1.76-1.69 (m, 4H), 1.60-1.53 (m, 4H), 1.05-0.95 (m, 12H); ¹³C NMR (100 MHz, CDCl₃): δ 157.1, 153.5, 152.0, 141.9, 138.7, 133.3, 121.3, 117.5, 115.2, 113.8, 112.0, 37.9, 32.7, 29.5, 28.3, 23.5, 22.9, 21.4, 21.2, 14.4, 14.3, 14.2, 13.8; HRMS (ESI⁺⁾ calculated for [C₂₄H₃₄N₂+H]⁺: 351.2800. found: 351.2805; IR (KBr): 2952, 2923, 1645, 1234 cm⁻¹.

Example 21

Yield: 88%; yellow solid; m.p. 110-115° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.16 (s, 1H), 6.75 (s, 1H), 2.77-2.71 (m, 4H), 2.51-2.41 (m, 7H), 1.76-1.69 (m, 4H), 1.60-1.53 (m, 4H), 1.05-0.95 (m, 12H); ¹³C NMR (100 MHz, CDCl₃): δ 157.1, 153.6, 152.1, 141.8, 138.7, 133.4, 121.3, 117.4, 115.2, 115.1, 113.8, 111.9, 34.9, 32.5, 31.8, 30.6, 30.4, 30.0, 27.1, 26.0, 23.1, 23.0, 22.9, 22.8, 22.6, 14.1, 14.0, 13.9, 13.8; HRMS (ESI⁺) calculated for [C₂₈H₄₂N₂+H]⁺: 407.3426. found: 407.3424; IR (KBr): 2954, 2923, 1643, 1234 cm⁻¹.

Example 22

Yield: 83%; scarlet red solid; m.p. 265-268° C.; ¹H NMR (500 MHz, CDCl₃): δ 7.52-7.50 (m, 5H), 7.47-7.38 (m, 2H), 7.28-7.19 (m, 10H), 7.12-7.06 (m, 5H), 7.05-6.96 (m, 5H), 6.92-6.88 (m, 2H), 6.80 (td, J=8.0, 2.0 Hz, 1H), 6.50-6.49 (m, 2H); ¹³C NMR (125 MHz, CDCl₃): δ 150.0, 149.3, 140.5, 138.6, 137.8, 137.6, 136.9, 136.8, 135.6, 135.2, 134.6, 131.8, 131.7, 131.2, 130.9, 130.2, 130.0, 129.7, 128.5, 128.2, 127.9, 126.9, 126.7, 126.6, 126.5, 125.9, 125.5, 124.9, 123.2, 121.8, 118.9, 117.5; HRMS (FAB⁺) m/z: MH⁺ calculated for C₄₉H₃₂N₂: 648.2565. found: 648.2563; IR (KBr): 3054, 2929, 2337, 1342 cm⁻¹.

Example 23

Yield: 68%; yellow solid; m.p. 265-268° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.41-7.30 (m, 5H), 7.29-7.21 (m, 8H), 7.20-7.14 (m, 6H), 7.08-7.06 (m, 2H), 6.78 (s, 1H), 6.34 (s, 1H), 3.36 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 152.1, 149.9, 143.0, 141.7, 141.4, 138.8, 138.2, 137.2, 136.5, 135.6, 131.4, 131.3, 130.1, 130.0, 129.8, 129.0, 128.5, 128.3, 128.1, 127.9, 127.8, 127.4, 127.2, 126.8, 126.6, 126.5, 126.4, 125.3, 120.9, 118.8, 118.3, 117.4, 116.5, 35.3; HRMS (FAB⁺) calculated for C₃₆H₂₆N₂: 486.2096. found: 486.2099; IR (KBr): 3054, 2929, 2337, 1342 cm⁻¹.

Influence of Catalyst, Oxidant and Solvent Examples 1a-1i and Comparative Example

Example 1 was repeated using (Z)-N-hydroxybenzamidine, diphenylacetylene, and the catalysts, the oxidants and the solvents shown in Table 2. The results are also shown in Table 2.

TABLE 2 Ex. Catalyst Oxidant Solvent Yield (%) 1a [Cp*Rh(CH₃CN)₃](SbF₆)₂ Cu(OAc)₂ DMF 70 1b [Cp*Rh(CH₃CN)₃](SbF₆)₂ Cu(OAc)₂ o-xylene 64 1c [Cp*Rh(CH₃CN)₃](SbF₆)₂ Cu(OAc)₂ dichloroethane 58 1d [Cp*Rh(CH₃CN)₃](SbF₆)₂ Cu(OAc)₂ acetonitrile 45 1e [Cp*Rh(CH₃CN)₃](SbF₆)₂ Cu(OAc)₂ acetic acid 50 1f [Cp*Rh(CH₃CN)₃](SbF₆)₂ Cu(OAc)₂•H₂O t-amylOH 62 1g [Cp*Rh(CH₃CN)₃](SbF₆)₂ Cu(OTf)₂ t-amylOH 15 1h [RhCp*Cl₂]₂(3 mol %) Cu(OAc)₂ t-amylOH 68 1i [RuCl₂(p-cymene)]₂ Cu(OAc)₂ t-amylOH 43 Comp. Ex. Pd(OAc)₂ Cu(OAc)₂ t-amylOH 0

As evidenced by the yield data shown in Table 2, the 1, 9-diazaphenalene derivative obtained in Example 1 may also be obtained using a rhodium-containing complex or a ruthenium-containing complex as a catalyst and using various solvents. However, the 1,9-diazaphenalene derivative obtained in Example 1 may not be obtained using a palladium-containing complex as a catalyst.

Synthesis (II) of 1,9-Diazaphenalene Derivative Examples 24-37

0.3 mmol of a benzonitrile compound of formula (IV), 1.5 mmol of an amine compound of formula (V), 0.66 mmole of an alkyne compound of formula (II), 4.0 mol % of [Cp*Rh(CH₃CN)₃](SbF₆)₂ (Cp* represents pentamethylcyclopentadienyl), and 1.35 mmol (4.5 equivalents) of copper (II) acetate were added into a sealed tube. The sealed tube was then evacuated and purged with nitrogen gas three times. 3 ml of 2-methyl-2-butanol was subsequently added into the sealed tube via a syringe under a nitrogen atmosphere to obtain a reaction mixture, which was stirred at 130° C. for 18 hours. The mixture was then cooled and diluted with CH₂Cl₂ (10 ml), followed by filtration through a Celite pad. The Celite pad was washed with CH₂Cl₂ (50 ml) to obtain a filtrate. The filtrate was concentrated in vacuo and the residue was purified by a silica gel column using hexane-EtOAc (5-15%) as eluent to give a product of formula (III).

The definitions of R¹, R², R³, X, R, Y¹, and Y² in formulae (I), (II), and (III) in Examples 24-37 are listed in Table 3.

TABLE 3 Formula Formula Formulae (IV) (V) (II) and (III) Formula (III) Ex. R¹ R² R³ X R R¹ R² R³ Y¹ and Y² 24 H H H Me Ph H H H Y¹ = Me; Y² = Ph 25 H Me H Me Ph H Me H 26 H tBu H Me Ph H tBu H 27 H F H Me Ph H F H 28 H Cl H Me Ph H Cl H 29 H Br H Me Ph H Br H 30 H CF₃ H Me Ph H CF₃ H 31 H N(Me)₂ H Me Ph H N(Me)₂ H 32 H Ph H Me Ph H Ph H 33 H CO₂Me H Me Ph H CO₂Me H 34 H COMe H Me Ph H COMe H 35 H CHO H Me Ph H CHO H 36 H H H Pr Ph H H H Y¹ = Pr; Y² = Ph 37 H H H H Ph H H H

The products obtained in Examples 24-37 were identified and the results are shown below.

Example 24

Yield: 68%; yellow solid; m.p. 265-268° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.41-7.30 (m, 5H), 7.29-7.21 (m, 8H), 7.20-7.14 (m, 6H), 7.08-7.06 (m, 2H), 6.78 (s, 1H), 6.34 (s, 1H), 3.36 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 152.1, 149.9, 143.0, 141.7, 141.4, 138.8, 138.2, 137.2, 136.5, 135.6, 131.4, 131.3, 130.1, 130.0, 129.8, 129.0, 128.5, 128.3, 128.1, 127.9, 127.8, 127.4, 127.2, 126.8, 126.6, 126.5, 126.4, 125.3, 120.9, 118.8, 118.3, 117.4, 116.5, 35.3; HRMS (FAB⁺) calculated for C₃₆H₂₆N₂: 486.2096. found: 486.2099; IR (KBr): 3054, 2929, 2337, 1342 cm⁻¹.

Example 25

Yield: 74%; yellow solid; m.p. 251-255° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.41-7.30 (m, 5H), 7.29-7.21 (m, 8H), 7.20-7.14 (m, 5H), 7.08-7.06 (m, 2H), 6.78 (s, 1H), 6.34 (s, 1H), 3.37 (s, 3H), 2.17 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 152.1, 149.9, 143.0, 141.7, 141.4 138.8, 138.2, 137.2, 136.5, 135.6, 131.4, 131.3, 130.1, 130.0, 129.8, 129.0, 128.5, 128.3, 128.1, 127.9, 127.8, 127.4, 127.2, 126.8, 126.6, 126.5, 126.4, 125.3, 120.9, 118.8, 118.3, 117.4, 116.5, 35.1, 22.4; HRMS (EI⁺) calculated for C₃₇H₂₈N: 500.2252. found: 500.2250; IR (KBr): 3054, 2931, 2337, 1342 cm⁻¹.

Example 26

Yield: 80%; yellow solid; m.p. 276-280° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.57 (d, J=6.4 Hz, 1H), 7.49-7.31 (m, 5H), 7.29-7.14 (m, 12H), 7.08-7.06 (m, 2H), 6.80 (s, 1H), 6.57 (s, 1H), 3.34 (s, 3H), 1.16 (s, 9H); ¹³C NMR (100 MHz, CDCl₃): δ 154.2, 152.0, 149.8, 142.7, 141.7, 141.4 138.8, 138.2, 137.2, 136.5, 135.6, 131.4, 131.3, 130.1, 130.0, 129.8, 129.0, 128.5, 128.3, 128.1, 127.9, 127.8, 127.4, 127.2, 126.8, 126.6, 126.5, 126.4, 125.3, 120.9, 118.8, 118.3, 117.4, 116.5, 35.4, 31.0; HRMS (EI⁺) calculated for C₄₀H₃₄N₂: 542.2722. found: 542.2724; IR (KBr): 3054, 2931, 2337, 1319 cm⁻¹.

Example 27

Yield: 77%; yellow solid; m.p. 176-180° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.53 (t, J=7.6 Hz, 2H), 7.46-7.32 (m, 4H), 7.28-7.19 (m, 9H), 7.08 (dd, J=7.6, 0.8 Hz, 1H), 6.97-6.88 (m, 4H), 6.67 (dd, J=8.0, 2.4 Hz, 1H), 6.23 (dd, J=8.0, 2.4 Hz, 1H), 3.43 (s, 3H); ¹³C NMR (100 MHz, CDCl₃) δ 164.9 (d_(C-F), J=244.8 Hz), 151.5, 150.9, 144.1, 141.9, 141.3, 139.9, 139.8, 138.2, 136.6, 135.1, 134.8, 132.6, 131.9, 131.3, 130.1, 130.0, 129.8, 129.5, 128.9, 128.7, 128.5, 128.1, 127.9, 127.8, 127.4, 127.2, 126.9, 126.8, 126.5, 126.3, 125.5, 118.3, 105.7 (d_(C-F), J=27.6 Hz), 103.5 (d_(C-F), J=24.2 Hz), 35.3; HRMS (EI⁺) calculated for C₃₆H₂₅FN₂: 504.2002. found: 504.2010; IR (KBr): 3054, 2932, 1350, 1126 cm⁻¹.

Example 28

Yield: 71%; yellow solid; m.p. 234-237° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.55-7.47 (m, 3H), 7.43-7.33 (m, 4H), 7.32-7.16 (m, 11H), 7.12 (d, J=7.6 Hz, 2H), 7.02 (s, 1H), 6.53 (s, 1H), 3.43 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 151.6, 151.0, 144.1, 141.2, 140.4, 138.4, 138.0, 137.9, 136.3, 135.0, 134.7, 131.3, 131.2, 130.0, 129.9, 129.8, 129.7, 128.9, 128.7, 128.5, 128.3, 128.2, 128.1, 127.2, 126.9, 126.8, 120.7, 118.7, 117.9, 116.3, 114.9, 35.3; HRMS (EI⁺) calculated for C₃₆H₂₅ClN₂: 520.1706. found: 520.1709; IR (KBr): 3054, 2923, 1342, 1126, 995 cm⁻¹.

Example 29

Yield: 68%; yellow solid; m.p. 210-212° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.65 (t, J=7.6 Hz, 1H), 7.49-7.25 (m, 5H), 7.23-7.11 (m, 12H), 7.08 (dd, J=8.4 Hz, 2H), 6.67 (d, J=8.0 Hz, 1H), 6.23 (dd, J=8.0 Hz, J=2.4 Hz, 1H), 3.44 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 152.2, 149.7, 142.8, 141.5, 138.6, 137.1, 136.5, 135.4, 134.8, 134.7, 131.3, 131.2, 130.0, 129.9, 129.8, 129.6, 128.9, 128.5, 128.3, 128.0, 127.7, 127.2, 126.8, 126.7, 126.5, 121.2, 120.4, 118.5, 117.3, 115.2, 35.2; HRMS (EI⁺) calculated for C₃₆H₂₅BrN₂: 564.1201. found: 564.1209; IR (KBr): 3054, 2931, 1565, 1334, 956 cm⁻¹.

Example 30

Yield: 78%; yellow solid; m.p. 278-282° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.47-7.35 (m, 5H), 7.30-7.25 (m, 8H), 7.24-7.21 (m, 5H), 7.19 (d, J=1.6 Hz, 1H), 7.13-7.11 (m, 2H), 6.70 (d, J=1.2 Hz, 1H), 3.46 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 151.7, 151.1, 144.2, 141.1, 139.1, 137.7, 136.2, 135.0, 133.0 (q, J=256.6 Hz), 131.3, 131.1, 131.0, 130.3, 130.1, 129.7, 128.9, 128.8, 128.6, 128.4, 128.2, 127.5, 127.3, 127.0, 126.9, 121.8, 121.4, 118.5, 113.8 (d, J=3.8 Hz), 110.6 (d, J=3.0 Hz), 35.4; HRMS (EI⁺) calculated for C₃₇H₂₅F₃N₂: 554.1970. found: 554.1972; IR (KBr): 3062, 2923, 2337, 1319 cm⁻¹.

Example 31

Yield: 72%; yellow solid; m.p. 252-256° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.40-7.30 (m, 5H), 7.29-7.20 (m, 8H), 7.20-7.14 (m, 5H), 7.08-7.04 (m, 2H), 6.77 (s, 1H), 6.33 (s, 1H), 3.37 (s, 3H), 2.79 (s, 6H); ¹³C NMR (100 MHz, CDCl₃): δ 152.1, 149.9, 143.0, 141.7, 141.4 138.8, 138.2, 137.2, 136.5, 135.6, 131.4, 131.3, 130.1, 130.0, 129.8, 129.0, 128.5, 128.3, 128.1, 127.9, 127.8, 127.4, 127.2, 126.8, 126.6, 126.5, 126.4, 125.3, 120.9, 118.8, 118.3, 117.4, 116.5, 35.1, 22.4; HRMS (EI⁺) calculated for C₃₈H₃₁N₃: 529.2518. found: 529.2521; IR (KBr): 3054, 2932, 2333, 1342 cm⁻¹.

Example 32

Yield: 82%; yellow solid; m.p. 271-274° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.41-7.30 (m, 5H), 7.29-7.21 (m, 8H), 7.20-7.10 (m, 10H), 7.08-7.06 (m, 2H), 6.78 (s, 1H), 6.34 (s, 1H), 3.43 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 152.1, 149.9, 143.0, 141.7, 141.4, 138.8, 138.2, 137.2, 136.5, 135.6, 135.2, 134.6, 131.4, 131.3, 130.1, 130.0, 129.8, 129.0, 128.5, 128.3, 128.1, 127.9, 127.8, 127.4, 127.2, 126.8, 126.6, 126.5, 126.4, 125.3, 120.9, 118.8, 118.3, 117.4, 116.5, 35.3; HRMS (EI⁺) calculated for C₄₂H₃₀N₂: 562.2409. found: 562.2407; IR (KBr): 3054, 2929, 2337, 1342 cm⁻¹.

Example 33

Yield: 65%; yellow solid; m.p. 263-267° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.64 (d, J=1.6 Hz, 1H), 7.38-7.34 (m, 5H), 7.34-7.30 (m, 1H), 7.26-7.22 (m, 8H), 7.20-7.15 (m, 7H), 3.71 (s, 3H), 3.36 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 167.3, 166.8, 152.0, 150.7, 143.6, 141.3, 138.9, 138.0, 137.7, 137.0, 136.9, 135.2, 132.2, 130.6, 130.4, 130.1, 129.9, 128.7, 128.6, 128.5, 128.2, 128.1, 127.9, 127.8, 127.5, 126.9, 126.7, 126.6, 126.2, 122.9, 122.0, 118.8, 115.0, 52.1, 35.3; HRMS (EI⁺) calculated for C₃₈H₂₈N₂O₂: 544.2151. found: 544.2158; IR (KBr): 3054, 2923, 2337, 1750, 1357 cm⁻¹.

Example 34

Yield: 72%; yellow solid; m.p. 274-277° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.52 (d, J=1.2 Hz, 1H), 7.41-7.29 (m, 6H), 7.24-7.13 (m, 12H), 7.05 (d, J=7.2 Hz, 2H), 6.99 (d, J=1.2 Hz, 1H), 3.38 (s, 3H), 2.32 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 199.0, 151.9, 150.7, 143.7, 141.2, 139.1, 138.0, 137.2, 136.5, 136.2, 135.2, 131.2, 131.1, 130.1, 129.9, 128.7, 128.5, 128.2, 128.1, 127.9, 127.3, 127.0, 126.8, 122.0, 118.9, 117.9, 113.6, 35.4, 29.6, 26.8; HRMS (EI⁺) calculated for C₃₈H₂₈N₂O: 528.2202. found: 528.2210; IR (KBr): 3054, 2932, 1680, 1343, 1203 cm⁻¹.

Example 35

Yield: 86%; yellow solid: m.p. 262-266° C.; ¹H NMR (400 MHz, CDCl₃): δ 9.79 (s, 1H), 7.45 (d, J=1.2 Hz, 1H), 7.43-7.37 (m, 5H), 7.34-7.30 (m, 1H), 7.26-7.22 (m, 8H), 7.20-7.15 (m, 7H), 3.41 (s, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 193.3, 152.2, 151.1, 144.0, 141.1, 139.4, 137.8, 137.7, 136.4, 135.1, 131.2, 131.1, 130.1, 129.8, 128.9, 128.6, 128.3, 128.2, 127.4, 127.1, 126.9, 122.6, 122.2, 121.1, 118.9, 113.2, 35.5; HRMS (EI⁺) calculated for C₃₇H₂₆N₂O: 514.2045. found: 514.2049 IR (KBr): 3054, 2923, 1620, 1342, 950 cm⁻¹.

Example 36

Yield: 73%; yellow solid; m.p. 244-248° C.; ¹H NMR (400 MHz, CDCl₃): δ 7.39-7.26 (m, 5H), 7.25-7.16 (m, 12H), 7.14-7.02 (m, 4H), 6.96 (d, J=8.0 Hz, 1H), 6.45 (bs, 1H), 3.89 (bs, 2H), 1.74 (q, J=7.6 Hz, 2H), 0.73 (t, J=7.6 Hz, 3H); ¹³C NMR (100 MHz, CDCl₃): δ 151.4, 149.6, 142.8, 141.7, 139.3, 138.8, 137.3, 136.6, 135.3, 131.4, 131.2, 131.1, 130.2, 130.1, 128.6, 128.3, 127.9, 127.8, 127.1, 126.6, 126.4, 121.1, 120.6, 118.6, 117.3, 115.0, 48.1, 29.6, 21.1, 11.2; HRMS (EI⁺) calculated for C₃₈H₃₀N₂: 514.2409. found: 514.2412; IR (KBr): 3054, 2932, 2337, 1343 cm⁻¹.

Example 37

Yield: 15%; scarlet red solid; m.p. 265-268° C.; ¹H NMR (500 MHz, CDCl₃): δ 7.52-7.50 (m, 5H), 7.47-7.38 (m, 2H), 7.28-7.19 (m, 10H), 7.12-7.06 (m, 5H), 7.05-6.96 (m, 5H), 6.92-6.88 (m, 2H), 6.80 (td, J=8.0, 2.0 Hz, 1H), 6.50-6.49 (m, 2H); ¹³C NMR (125 MHz, CDCl₃): δ 150.0, 149.3, 140.5, 138.6, 137.8, 137.6, 136.9, 136.8, 135.6, 135.2, 134.6, 131.8, 131.7, 131.2, 130.9, 130.2, 130.0, 129.7, 128.5, 128.2, 127.9, 126.9, 126.7, 126.6, 126.5, 125.9, 125.5, 124.9, 123.2, 121.8, 118.9, 117.5; HRMS (FAB⁺) m/z: MH⁺ calculated for C₄₉H₃₂N₂: 648.2565. found: 648.2563; IR (KBr): 3054, 2929, 2337, 1342 cm⁻¹.

Determination of Absorption and Fluorescence Spectra:

An ultraviolet-visible absorption spectrum (solvent: dichloromethane; concentration: 10⁻⁵ M) and a fluorescence spectrum (solvent: dichloromethane; concentration: 10⁻⁴ M; excitation wavelength: 400 nm) for each of the 1,9-diazaphenalene derivatives obtained in Examples 9, 10, 12 and 18 were obtained using a Hitachi F-7000 fluorescence spectrophotometer. The results are shown in Table 4 and FIG. 1.

TABLE 4 Absorption Molar peak extinction Fluorescence wavelength coefficient peak wavelength Ex. (nm) (M⁻¹ cm⁻¹) (nm) 9 396, 434 18450, 18260 529 10 416 19700 519 12 392, 448 17290, 18720 517 18 430 13310 508

As shown in Table 4 and FIG. 1, the fluorescence peak wavelengths of the 1,9-diazaphenalene derivatives obtained in Examples 9, 10, 12 and 18 range from 508 to 529 nm, and the FWHM (full width at half maximum) of the 1,9-diazaphenalene derivative obtained in Example 12 is about 75 nm, indicating that the 1,9-diazaphenalene derivative of the disclosure may emit green fluorescence after being excited.

In view of the aforesaid, the 1,9-diazaphenalene derivative of the disclosure, which contains a plurality of fused aryl rings and which is highly substituted, may emit fluorescence after being excited, and is thus suitable for use as a fluorescent material for an organic light emitting diode. Furthermore, the 1,9-diazaphenalene derivative of the disclosure may be manufactured in a high yield via a simple one-pot reaction.

While the disclosure has been described in connection with what is(are) considered the exemplary embodiment(s), it is understood that this disclosure is not limited to the disclosed embodiment(s) but is intended to cover various arrangements included within the spirit and scope of the broadest interpretation so as to encompass all such modifications and equivalent arrangements. 

What is claimed is:
 1. A 1,9-diazaphenalene derivative represented by formula (III),

where each R independently represents a C₁-C₁₀ linear or branched alkyl group, or a 5-6 membered aryl or heteroaryl group which is unsubstituted or substituted with a C₁-C₁₀ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ haloalkyl group or a halo group; each of R¹, R², and R³ independently represents hydrogen, a C₁-C₁₀ linear or branched alkyl group, a C₁-C₁₀ alkoxy group, a C₁-C₆ haloalkyl group, an unsubstituted or C₁-C₁₀ alkyl group-substituted amino group, a halo group, a C₆-C₁₈ aryl group,

in which R⁴ represents a C₁-C₁₀ alkyl group, or

in which R⁵ represents hydrogen or a C₁-C₁₀ alkyl group; Y¹ represents hydrogen, or a C₁-C₁₀ linear or branched alkyl group; Y² represents R; or Y¹ and Y² are combined to forma 6-membered ring moiety represented by

where each of R⁶ and R⁷ independently represents a thio group, a heteroalkyl group, or a C₁-C₁₀ linear or branched alkyl group, or R⁶ and R⁷ are combined to form a 5-6 membered aryl or heteroaryl group represented by

which is unsubstituted or substituted with a C₁-C₁₀ alkyl group, a C₁-C₆ alkoxy group, a C₁-C₆ haloalkyl group or a halo group.
 2. The 1,9-diazaphenalene derivative according to claim 1, wherein the 5-6 membered aryl or heteroaryl group is represented by


3. The 1,9-diazaphenalene derivative according to claim 1, wherein each R is independently selected from the group consisting of phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-bromophenyl, 4-trifluoromethylphenyl and 2-thienyl.
 4. A process for manufacturing a 1,9-diazaphenalene derivative according to claim 1, comprising the step of subjecting a benzamidine derivative of formula (I)

where X represents hydrogen, hydroxyl, or a C₁-C₁₀ linear or branched alkyl group, and an alkyne compound of formula (II)

to a catalystic reaction in the presence of an oxidant and a catalyst selected from the group consisting of a rhodium-containing complex and a ruthenium-containing complex.
 5. The process according to claim 4, wherein a molar ratio of the benzamidine derivative to the alkyne compound ranges from 1:2 to 1:3.5.
 6. The process according to claim 5, wherein the molar ratio of the benzamidine derivative to the alkyne compound ranges from 1:3 to 1:3.5.
 7. The process according to claim 4, wherein the oxidant is selected from the group consisting of copper (II) acetate, copper (II) acetate monohydrate, and copper trifluoromethanesulfonate.
 8. The process according to claim 4, wherein the rhodium-containing complex is selected from the group consisting of [Cp*Rh(CH₃CN)₃](SbF₆)₂ and [RhCp*Cl₂]₂, wherein Cp* represents pentamethylcyclopentadienyl.
 9. The process according to claim 4, wherein the ruthenium-containing complex is [RuCl₂(p-cymene)]₂, wherein Cp* represents pentamethylcyclopentadienyl.
 10. The process according to claim 4, wherein the catalystic reaction is conducted in the presence of an organic solvent.
 11. The process according to claim 10, wherein the organic solvent is selected from the group consisting of 2-methyl-2-butanol, dimethylformamide, o-xylene, dichloroethane, acetonitrile and acetic acid.
 12. The process according to claim 4, wherein X represents hydroxyl.
 13. A process for manufacturing a 1,9-diazaphenalene derivative according to claim 1, comprising the step of subjecting a benzonitrile compound of formula (IV)

an amine compound of formula X—NH₂ (V), where X represents hydrogen, hydroxyl or a C₁-C₁₀ linear or branched alkyl group, and an alkyne compound of formula (II)

to a catalystic reaction in the presence of an oxidant and a catalyst selected from the group consisting of a rhodium salt and a ruthenium salt.
 14. The process according to claim 13, wherein a molar ratio of the benzonitrile compound to the alkyne compound ranges from 1:2 to 1:3.5. 